DE2013316A1 - - Google Patents

Description

DR.-ING. BY KREISLER DR.-ING. BEAUTIFUL FOREST DR.-ING. TH. MEYER DR. FUES DIPL.-CHEM. ALEK VON KREISLER DIPL.-CHEM. CAROLA KELLER DR.-ING. KLDPSCH

COLOGNE 1, DEICHMANNHAUS

February 26, 197ο. Fu / bz. ....;

Cologne rubber thread factory formerly Ferd. Kohlstadt & Co Cologne-Deutz, Deutz-Mältieimer-Strasse 127 - 129

Uncrosslinked, linear polyurethanes with improved properties and processes for their manufacture .

^: The "invention relates to new non-crosslinked y: linear'-PoIy ^. CS ^ f, - ^ urethane / !. which can be processed thermoplastically and from which moldings of high strength can be produced, which can be characterized by extremely low permanent deformation. The invention also relates to

* ■ a process for the production of the new polyurethanes. ;.

Known are, uncrosslinked, linear polyurethanes based on bifunctional, hydroxyl and optionally amino groups and / or mercapto groups, preferably compounds ^{containing two hydroxyl groups Λ} with molecular weights between 1000 and 10,000; preferably 1,500 to 3OOO, or mixtures of such mixtures.

..bindersi, aliphatic and / or aromatic.Diiso - ":;. ;; cyanates.and bifunctional, hydroxyl ;. amino and / - ': <■ ■ ^: or mercapto groups, preferably compounds containing two hydroxyl groups with molecular weights below 1000 , preferably less than 500, or mixtures of such compounds. As a rule, equimolar or almost equimolar amounts of diisocyanate and hydroxyl, "amino and" or mer-

• kaptogruppen aufvdsende connections implemented, whereby one- more appropriately with a very low over-

0 0 9840/2256

Polyurethanes can be achieved.

A major disadvantage of the known linear polyurethanes is that the moldings produced from them have a very high set after tensile or Have compressive stress, relatively independently on the respective composition of the linear polyurethane and its other mechanical properties: that is, although generally the higher the set is. The softer the material is, even fairly hard linear polyurethanes show a fairly high permanent set; it often lies many times higher than that of unfilled natural rubber vulcanized products. Despite this disadvantage ■ linear polyurethanes are manufactured and processed in the rubber industry because of their special properties Advantage of the diverse and easy processability due to the thermoplastic behavior these polyurethanes. '

Also known are polyurethanes which, with the use of reactive double bonds, are also known Starting compounds, for example using glycerol 1-allyl ether, are prepared. Even If these polyurethanes initially have a linear structure, they are only thermoplastic to a very limited extent processable, because they are preferably made by sulfur or by peroxide during processing converted into networked products.

Moldings made from such polyurethanes have a compared to the known, linear polyurethanes has a lower set, but their processing has disadvantages compared to that of real thermoplastics tied together. Before the shaping can take place,

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shot than works with a little less diisocyanate. Experience has shown that a smaller amount of diisocyanate is used no sufficiently high molecular weights achieved and thus finished products with insufficient mechanical Properties obtained, while larger amounts of diisocyanate usually with the formation of allophanate or biuret bonds cause crosslinking reactions, As a result, such polyurethanes can only be processed thermoplastically to a very limited extent and, moreover, mostly become insoluble, so that they cannot be processed from the solution either.

The physical properties of the moldings produced from linear polyurethanes depend on the Structure of the starting compounds used in each case depends on the quantitative proportion of diisocyanate or, which is practically the same because of the equivalence of the starting compounds, of the respective quantitative ratio the higher molecular weight and the lower molecular weight compounds. The greater the proportion of higher molecular weight Connection, the greater the ductility in general. In contrast, the greater the proportion of low molecular weight Connection (chain extender), the higher the strength and the harder and less The moldings produced from such polyurethanes are stretchable. Since both soft rubber-like and Hard polyurethanes can also be used with advantage for the various purposes of application are in principle Compositions between the two borderline cases of the exclusive use of long-chain Starting compounds and the exclusive use of short-chain starting compounds, technically interesting, especially because of the structure, but to a certain extent also because of the molecular weight of the output connections used in each case have a further influence on the properties of the

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the crosslinking reagents and, if necessary, accelerators must first be thoroughly applied to the roller or in the Kneaders are mixed into the polyurethane mass. The storage stability of such mixtures is limited. Often the crosslinking reaction starts already during the Shaping a, so that certain measures must be taken to prevent premature vulcanization. In many cases, the heating time required for full vulcanization has a detrimental effect on the Capital expenditure, mostly also on the number of pieces of production. It is particularly disadvantageous that the waste generated during polyurethane processing or do not reprocess defective moldings let, whereby the manufacturing costs are increased overall. . .

Non-linear polyurethanes are also known. These are through-shared by more than two-functional Isocyanates, for example triphenylmethane triisocyanate, and / or by using more as two-functional starting compounds with hydroxyl and / or amino groups, for example trimethylolpropane, obtained. The non-linear polyurethanes include also those which - even when using exclusively bifunctional starting compounds - through use from excess amounts of diisocyanate can be obtained, causing crosslinking of the molecules occurs through allophanate and / or biuret bonds. This "crosslinking" caused by excess diisocyanate can occur during the production of a polyurethane precursor, especially in Use of temperatures above 70 ° C; the possibly subsequent addition of a bifunctional chain extender containing hydroxyl and / or amino groups leads to equivalence. then im generally no longer leads to a linear molecular structure.

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Crosslinked polyurethanes are not or only extremely difficult to process thermoplastically, they can usually not out of the solution, often not even when using highly polar solvents such as dimethylformamide, are processed. They are therefore preferably used as castable polymers by one initially still fusible prepolymer immediately before shaping with a crosslinking chain extender mixes and lets this mixture react in the mold. Particularly disadvantageous with this method In contrast to the production of moldings from thermoplastic material, this is often very short Only a few minutes pot life and no less, disadvantageously, the already mentioned, cost-increasing one Fact that waste and faulty production cannot be reused.

The invention relates to a process for the preparation of uncrosslinked, linear polyurethanes Implementation of a) bifunctional. Hydroxyl and optionally amino groups and / or mercapto groups, preferably compounds containing two hydroxyl groups and having molecular weights between 1000 and 10,000, preferably 1500 to 3OOO, or mixtures of such compounds, b) aliphatic and / or aromatic diisocyanates and c) bifunctional, hydroxyl, amino and / or mercapto groups - preferably two hydroxyl groups - containing compounds with molecular weights below 1000, preferably below 500, or mixtures of such compounds, characterized in that that partially or completely such starting compounds a, b and / or c are used which at least have a grouping of atoms, which by a practical rigid linkage of at least two aliphatic and / or aromatic ones that are not in one plane Wrestling is formed.

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2013310

The production of the new polyurethanes can be carried out either in a single-stage or in a multi-stage process will; in the last-mentioned case, the amount used to prepare prepolymers containing isocyanate groups is required molar excess of b over a and c not more than 100 percent, but on the end product based on no more than 6 percent, preferably no more than 3 percent.

The invention also relates to the uncrosslinked, linear polyurethanes produced in this way,

As a result of the fact, known to the person skilled in the art, that linear polyurethanes have a very high set, It was an extremely surprising finding that by incorporating compounds above of the type described in a polyurethane whose permanent deformation is remarkably reduced will. In many cases, the set is even below that of unfilled natural rubber vulcanizates. There is therefore no doubt that polyurethanes of this type on the one hand because of their advantageous Processability as a thermoplastic material and on the other hand because of its unusually low Deformation residue represent a technical advance.

Obviously, the atom groupings, which by an almost rigid connection of at least two aliphatic and / or aromatic rings not lying in one plane are formed, a restriction the mobility of the chain in such a way that the movable ones completely slide past each other aliphatic chain segments in the state of tension to a greater extent than exclusively through the hydrogen bonds the hard, urethane groups -

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the chain segments is prevented. It is likely that a state has thereby been reached which is advantageous enables thermoplastic processing known from uncrosslinked, linear polyurethanes, which at the same time also offers the advantage of low permanent deformation that was previously only possible with cross-linked, non-linear polyurethanes.

As compounds with atom groupings, which by a practically rigid connection of at least two, aliphatic and / or aromatic rings that do not lie in one plane are formed are special those starting compounds a, b and / or c suitable which contain at least one polycyclic bridge ring system contain, which can also have one or more heteroatoms.

The incorporation of such polycyclic bridge ring systems in the starting compound a takes place exclusively through hydroxyl, Amino and / or mercapto groups, preferably through hydroxyl groups.

Such space-filling, three-dimensional ring structures can be found both in natural products and in synthetic products. A technical product which significantly reduces the set in polyurethanes and therefore for the production of the invention Polyurethanes can be used with advantage,

is for example tricyclodecanedimethylol- (5,2,1,0, ')

CH ₂ OH

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By dimerizing I, for example, the Compound II obtained as starting compound c with two polycyclic bridge ring systems:

CH ₂ -O- CH ₂

or by reacting I with adipic acid, the starting compound a can be, for example, a polyester manufacture with many polycyclic bridge ring systems. '

Such starting compounds a, b and / or c are incorporated into the polyurethane via two reactive compounds functional groups. The latter are preferably hydroxyl, optionally amino and / or mercapto groups (preferred Starting compounds a and c). But you can also only use isocyanate groups (starting compound b) be. The amino groups are preferably primary, optionally also secondary amino groups. The functional Groups can be located at any point in the polycyclic bridge ring system; but they can also go through a radical which is not itself reactive, for example an alkyl radical which may contain heteroatoms in non-reactive form, for example oxygen in ether bond, with the polycyclic bridge ring system be connected.

Other compounds of this type are: bicyclo- (2.2, l) -heptanediol- (2.5), 2,6-methylene-bicyclo- (0,3,3) -octanediol- (l, 5), 2,5-methylenebicyclo- (0,3,4) -nonanediol- (7,8), 1,7,7,1 ', 7 ¹ ^ ¹ -hexamethyl- (2,2') -binorbonyldiol- ( 2,2 '), 4,7,7,4', 7 ', 7 ^! -Hexamethyl- · (2.2 ^l ) -binorbonyldithiol - (^, 3 ^t ), 9.9'-dimethyl-3,3 · - dihydroxy-dinortropyl, 2,6-diamino-bicyclo- (1,5,3) - nonane,

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1,6-methano- (10) -annulene diethylol, bicyclo- (2, j5, j5) -decanediol, Nortricyclendiol, Adamantandiol, 1,5-Dimethyladamantandiol-2,7 » Bicyclo- (2,2,2) -octanediol, norcodeine, chimonanthine, catharosine, calycanthine or Chenodeoxycholine methyl ester. Diamines with polycyclic bridge ring systems can be obtained by reaction convert with phosgene into the corresponding diisocyanates.

Furthermore, as compounds with atomic groups, which by a practically rigid linkage of at least two aliphatic and / or aromatic rings that are not in one plane are formed are special such starting compounds a, b and / or c are suitable, the at least one sterically hindered atom group of the formula III

R.
Z

contain, the rings X and Y at least 5-membered, are preferably 6-membered and aliphatic and / or aromatic, containing one or more heteroatoms can, and where

A) Z is a -0-, -S-, -SO-, -SO ₂ -, -CO-, or -CH ₂ group and at least one of the radicals R is an alkyl group with 1-18 carbon atoms, a cycloalkyl - Or an aryl group (which groups can also be bonded to the ring X or Y via an oxygen or sulfur atom), a dialkylamino group with 2-24 C atoms, a nitro group or a halogen atom, while the other radicals R are hydrogen atoms , or where all the radicals R can also be hydrogen atoms, provided that the rings X and Y are aliphatic and Z is a -0-, -CO- or -CH ₂ ~ group,

G09840 / 22S5

- ίο -

B) Z denotes a -CHR ₁ - or -CR ^ group in which R, or R, and Rp are each an alkyl or cycloalkyl radical with 1 - 12 carbon atoms or R. and R _{2 are} a common cycloaliphatic ring, and here the radicals R have the meaning given under A) or all radicals R are hydrogen atoms, or

C) the rings X and Y are directly connected to one another and the radicals R have the meaning mentioned under A) or all radicals R can be hydrogen atoms, provided that the rings X and Y are aliphatic.

The steric hindrance of the atom grouping according to formula III is brought about either by at least one of the radicals R or by Z, optionally also by the radical R ₁ or by the radicals R ₁ and R ₂ . These residues can support each other in their effectiveness. Both the radicals R and the radicals R, and can be identical or dissimilar.

The incorporation of such sterically hindered atom groups into the starting compound a takes place exclusively by hydroxyl, amino and / or mercapto groups belonging to this atom group, preferably through Hydroxyl groups.

The incorporation of such starting compounds a, b and / or c into the polyurethane takes place through two reactive functional groups. The latter are hydroxyl, amino and / or mercapto groups (preferred starting compounds • a and c) or isocyanate groups (starting compound b). In principle, hydroxyl groups are preferred. The amino groups can be primary or secondary; primary amino groups are preferred.

009640/2265

The functional groups required for incorporation into the polyurethane can be found directly on rings X and Y but not more than one functional group on a ring. You can in any ring position occur, also in ortho division to Z, if the last said ring position is not occupied by a radical R. Instead of directly on the ring, the functional Group are also located on a radical R of the ring X or Y, respectively. The incorporation of the sterically hindered atom group according to Formula III takes place in each case via the rings X and Y through a total of two reactive functional ones Groups.

The hydrogen atoms of rings X and / or Y can as far as they are not already substituted according to the description above, partially or completely by unreactive radicals, for example by alkyl radicals or halogen atoms. Such a radical can be heteroatoms in non-reactive form, for example Oxygen atoms in ether bonds, nitrogen atoms as tertiary amino groups or halogen atoms. If necessary, such a radical, which is itself non-reactive, can be one of the two, instead of the radical R carry functional groups required for incorporation into the polyurethane. Also count among the connections of the type described above, those compounds in which the rings X and / or Y are aliphatic and / or aromatic rings are present in condensed form. Such a fused-on ring can be part of one of the Be radicals R and / or have one of the two reactive functional groups. The hydrogen atoms Such fused-on rings can also be partially or completely substituted by non-reactive radicals are present. Such a residue can also be one of those required for incorporation into the polyurethane have functional groups.

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2013 318

The radicals R, and Rp, which are part of Z in the sterically hindered atom groups according to B), can contain heteroatoms in non-reactive form, for example oxygen atoms in ether linkage or halogen atoms. They can also have chain and / or ring-shaped side groups, optionally fused-on aliphatic and / or aromatic rings. These radicals R ₁ and R 2 do not contain any reactive functional groups.

If the functional groups required to incorporate the sterically hindered atom group into the polyurethane are located directly on the ring X or Y, occur the following special cases. Hydroxyl and mercapto groups on the benzene nucleus are known to react because of their acificification Effect of the benzene nucleus no longer or only insufficiently with isocyanate groups, so that compounds of this type are not suitable for polyurethane production. However, their functional derivatives are suitable, which have aliphatically or alicyclically bonded functional groups, very particularly the alkoxylated compounds. For example, one obtains by propoxylation of l.l-bis (4-hydroxyphenyl) cyclohexane in a simple manner the compound with the formula IV, the two aliphatic has bound hydroxyl groups:

HO-CH- CH ₂ - 0 - // \\ // \\ ο - CH ₅ - CH - OH

^^ V ^ ⁷ H ^

Furthermore, in compounds in which Z according to formula III has the meaning given under B) and thereby the Rings X and Y are benzene nuclei, optionally isocyanate groups present for incorporation into the polyurethane also not directly to the benzene nuclei, but rather

0 0-9 8 AO / 22 5 5

preferably to the rings via an aliphatic radical iX and Y bound.

In the following, those compounds are listed by way of example which have a sterically hindered atomic grouping according to formula III. The diphenols mentioned for the purpose of simplifying the designations are, as already mentioned, used as alkoxylated compounds. Diisocyanates (starting compound b) which can be obtained in a simple manner from the corresponding diamines by phosgenation are not listed; For example, the phosgenation of bis (2-methyl-4-aminocyclohexyl) methane gives the diisocyanate of the formula V:

OCN- (CH ₂ y- (V- NCO

h, c '; .

The compounds of group A) include, for example: 3.2'-dihydroxy-2.5-dimethyl-diphenyl ether, bis (4-hydroxy-2-methyl-5-isopropyl-phenyl) sulfide, Bis (2.5-dimethyl-4-hydroxyphenyl) sulfoxide, bis (4-hydroxy-2-methyl-phenyl) sulfone, bis (4-hydroxy-naphthyl-1) ketone, bis (2-ni "tro-4-hydroxyphenyl) methane, Bis (2-methyl-5-aminophenyl) sulfide, bis (2-methyl-4-methylamino-phenyl) ketone, 2-nitro-4,4'-diphenylmethane, 2-methyl-5.4'-diamino-diphenylmethane, bis (2.6-dimethyl-4-aminophenyl) methane, bis (2-methyl-4-mercapto-cyclohexyl) methane, Bis (4-hydroxynaphthyl-1) methane, bis (2-methyl-5-aminocyclohexyl) methane, Bis (4-hydroxy-cyclohexyl) methane, bis (4-aminocyclohexyl) methane, 1- (2.5-Dimethyl-3-hydroxy-cyclohexyl) -l- (4-hydroxy-cyclohexyl) ether and bis (4-hydroxy-decahy-.dro-naphthyl-1) ketone.

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The compounds of group B) include, for example; 1.1.-bis (2-methyl-4-hydroxyphenyl) butane, 1.1.-bis (4-aminopheny1) hep tan, 1.1-B i s (4-hydroxyphenyl) propane, l..l-bis (4-hydroxy-2-methyl-5-isopropyl-phenyl) ethane, 1- (4-hydroxycyclohexyl) -1- (4-hydroxyphenyl) ethane, 2.2.-bis (4-hydroxyphenyl) propane, 2.2-bis (4-hydroxycyclohexyl) propane, 2- (; 5-methyl-4-hydroxy-cyclohexyl) -2- (3-methyl-4-hydroxyphenyl) propane, 2.2-bis (4-aminocyclohexyl) propane, 2.2-bis (3-methyl-4-aminocyclohexyl) propane, 2.2-bis (2-methyl-5-hydroxyphenyl) propane, 2.2-bis (4-hydroxyphenyl) butane, 4.4-bis (4-hydroxyphenyl) -heptane, 2.2-bis (4-methylaminophenyl) propane, l.l.-bis (4-aminophenyl) cyclohexane, 1.1.-bis (4-hydroxyphenyl) cyclohexane, 1.1-bis (4-hydroxycyclohexyl) cyclohexane and 1-Me ethyl, 2,3-bis (4-hydroxyphenyl) cyclopentane.

The compounds of group C include, for example: 2-methoxy-4,4'-diamino-diphenyl, 2,2'-dimethyl-4.4 ^t diamino-diphenyl, 2,2'-dichloro-4,4'-diamino-diphenyl, 2,2'-diethoxy-4.4 ' -diamino-diphenyl, 2.2 ^f .5.5'-tetrachloro-4.4'-diamino-diphenyl, 2.2'.6.6'-tetrabromo-4.4 '.- diamino-diphenyl, 2.2'-dinitro-4.4'-diamino-diphenyl, 5.3'-Dirnethoxy-4.4'-diamino-6.6'-dichloro-diphenyl, 2.2 ^f -Bis (l-methyl-l-hydroxy-propyl) diphenyl, ^ .3'-dicyclohexyl-4.4'-dihydroxy-dinaphthyl- (ll), 2.2'-dimethyl-30 ^l -dihydroxy-5.5'-diisopropyl-dicyclohexyl, 3.3.3 ¹ .3'-tetramethyl-5.5'-dihydroxy-dicyclohexyl, l-isopropyl-2- (4-hydroxyphenyl) indanol- (5) , 4.4'-Di- ■ hydroxydicyclohexyl, 2.2'-dihydroxydicyclohexyl, 1.1'-dihydroxydicyclopentyl, 1-phenyl-S-amino ^ - (4-aminophenyl) -benzimidazoil and 2.2'-diamino-4.4'.6.6'-tetranitro-dipyridine - (5 5)

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- 17 -

- CH ₀ - CH - OH

C. f

CH,

Ό - CHo - CH - OH

CH,

As can be seen, for example, in the case of the compound according to formula IX, it is also possible to use compounds which have at least two different atom groupings in the molecule, each of which is represented by a practical rigid linkage of at least two aliphatic and / or aromatic ones that are not in one plane Rings are formed.

Finally, mixtures of compounds can also be used in the production of polyurethane, the atomic groups have within the meaning of the invention.

The starting compounds a and / or c are preferably used in the process according to the invention, where as starting compound a polyester, polyester amides, polyethers and / or polythioethers are preferably used will. For the preparation of the compound a, those compounds with at least one atomic grouping, which through a practically rigid connection of at least two aliphatic and / or aromatic rings is formed, used or concomitantly used as reactive functional Groups contain hydroxyl, amino and / or mercapto groups, preferably hydroxyl groups. In the cases that highly elastic moldings are to be produced from the polyurethanes, the procedure is advantageously as follows: that the atom group, which by a practically rigid linkage of at least two not in

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a plane lying aliphatic and / or aromatic rings is formed in the starting compound c is present. .

In addition to the compounds described above with at least one polycyclic bridge ring system and / or with at least one sterically hindered atomic grouping according to formula III, they are known to be suitable for polyurethane synthesis used compounds are used. In the case of the starting compound a, they are particularly suitable Polyesters, polyester amides, polyethers or polyethio ethers.

Linear polyesters are made from dicarboxylic acids in a known manner and dihydric alcohols or from oxycarboxylic acids or from their cyclic lactones. Polyesters made from aliphatic starting compounds are preferably suitable. By using diamines, Amino alcohols and / or aminocarboxylic acids or their cyclic lactams are obtained from polyester amides. The for A'ther and / or thioether groups can be used to prepare the polyesters or polyester amides used exhibit.

Examples of linear polyethers are the polymers of ethylene oxide, propylene oxide or tetrahydrofuran and their copolymers are listed. Also in question uniform or mixed polyethers come from glycols such as ethylene glycol, propylene glycol-1,2, butanediol-1,4, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol or 1,3-propylene glycol In addition, these include ethoxylated or propoxylated, optionally also mixed alkoxylated Glycols. Among the thiopolyethers are particularly the condensation products of thiodiglycol, if appropriate also mentioned as mixed condensates with other glycols.

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■ · - 21 -

The polyurethanes according to the invention can be used in a known manner as a processing aid or to improve or Cheaping of the moldings to be made from them plasticizers, fillers, dyes, lubricants, blowing agents, cell regulators, anti-aging agents, hydrolysis inhibitors, flame-retardant additives or fragrances are added. The admixing can be done in well-known Manner in suitable mixing units. If the additives are indifferent, they can be added at any point during the production of the polyurethane. the It can also be added to the dissolved polyurethane. After all, you can get such additives on the surface drum up the urethane granulate or powder.

The production of moldings from the polyurethanes according to the invention can be carried out by any known method Production of moldings made of thermoplastic material take place, for example the casting, calender, Press, extrusion or injection molding processes. The processing can also be done from the solution.

* ■

The moldings produced from the polyurethanes according to the invention have, as the following examples show, a very low permanent deformation, which has been proven exclusively through the use of compounds which have at least one atomic grouping, which by a practical rigid linkage of at least two aliphatic and / or aromatic rings not lying in one plane is formed, comes about, regardless of the composition of the polyurethane in question. Apart from this extremely important property improvement it was found, surprisingly, that

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- 22 -

In most cases, the strength of the molded body is also significantly improved without the Elongation at break experiences a considerable loss. This advantage must also be seen as a technical advance.

The test values given in the examples were based on standardized test methods used in practice:

1) on test bodies:

Normal climate according to DIN 50020

(Draft 8/67)

Tensile strength according to DIN 53504

Elongation at break according to DIN 53504

Tension at 300 %

Elongation according to DIN 53504

Shore A hardness according to DIN 53505

Rebound elasticity according to DIN 53512

The permanent elongation after 30 seconds or after minutes was referred to as a percentage change in length determined on the initial length on specimens torn according to DIN 53504.

2) on elastic threads:

Normal climate according to DIN 50020 (draft 8/67) Thread cross-section according to DIN 7720 sheet 2

(Draft 3/68)

Tensile strength according to DIN 7720 sheet 3

(Draft 3/68)

Elongation at break according to DIN 7720 sheet 3

(Draft 3/68)

The permanent elongation after 30 seconds was expressed as a change in length as a percentage, based on the initial length, determined after the return from an elongation of 400 percent.

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example 1

An adipic acid polyester with a molecular weight of 2000 (hydroxyl number = 56, acid number < ^{1.0) was thoroughly dehydrated for 4 hours at 100 °} C. in a vacuum (approx. 10 torr). To 0.05 mol = 100.0 g of this polyester in a glass vessel fitted with a stirrer and thermometer, 0.05 mol = 4.5 g of 1,4-butanediol and 0.15 mol = 29.5 g of tricyclodecanedimethylol (5 * 2 , 1.0, ') was added and the mixture was brought to 80 ° C. With vigorous stirring, 0.2p8 mol = 44.8 g of a mixture of 80 parts by weight of 2,4-tolylene diisocyanate and 20 parts by weight of 2,6-tolylene diisocyanate (hereinafter referred to as TDI 80/20 for short) were then added and the reaction product after 2 Poured into an aluminum jar (made of aluminum foil) for minutes. For complete Urnsetzung of the functional groups, the vessel was heated in an oven l8 hours at 100 ⁰ C. After cooling, a rubber-like, thermoplastically processable product was formed which had a softening point of around 170-180 ° C.

The linear polyurethane formed a fur on the hot roll when it was narrowed. Fillers and the like interfere without difficulty.

In the first comparative experiment, the amount of tricyclodecanedimethylol was decreased to 0.1 mol and accordingly doubled the amount of butanediol, while in the second comparative experiment butanediol was used exclusively instead of tricyclodecanedimethylol.

Round test specimens (diameter 65 mm, thickness 4 mm) were produced in the multi-stage press using 20.5 g of polyurethane in each case. Pressing time: 3 minutes; Compression pressure: I80 kg / cm j Temperature: 1 & O ° C. After being removed from the press the test specimens cooled rapidly and standard rings R 1 according to DIN 53504 punched out of them.

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The following test values were determined:

Comparative experiment example 1 1 2

Tensile strength

/ kp / cmV ² 79 197

Elongation at break Γ $ 7 550 610

Tension at JOQ %

Elongation / ~ kp / cm_7 J> k. -

Shore Α hardness 78

Rebound resilience /% 7 22

Permanent stretch after

20 seconds / "# / 3 6 16

Permanent stretch after

60 minutes Γ% 7

y ——

With high tensile strength and elongation at break, the permanent elongation was below that of unfilled natural rubber vulcanizates; the latter is generally found to be 3 to 6 percent.

The comparative experiment with a smaller amount of tricyclodecanedimethylol did not give quite as high strength and a slightly higher permanent elongation. The test specimens of the In contrast, the second comparative experiment without tricyclodecanedimethylol showed low strength and high permanent strength Strain.

Further comparative tests were carried out by replacing half of the butanediol amount of the polyurethane that was produced without tricyclodecanedimethylol with equimolar amounts of hexanediol. 1.6 or one third of the butanediol amount with equimolar amounts of 4,4'-diaminodiphenylmethane or 2.3 ^f - Dimethyl-4 _f 4 ^l -diaminodiphenylmethane was exchanged. In the order given above for the composition, the following test values were obtained:

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- 25 - '

Comparative tests -3 --4.-.- 5

activity / Hcp / cm

Tensile strength / Hcp / cm 7 110 116 112 Permanent elongation after. ■■; , J> 0 seconds ■ / ~% "J 21 J> 1 45

These experiments show that other starting compounds with hydroxyl groups or amino groups in contrast to for the according to the invention. Polyurethanes used Starting compounds no increase in tensile strength and do not cause any reduction in permanent set.

Example 2

Corresponding to Example I vh.rae a polyurethane

0.10 mole = 280.0 g of a polycaprolactone with the middle one Molecular weight of 2800

, 6.20 moles = 48.0 g of 2,2-bis (4-hydroxycyclohexyl) propane 0.20 mol = 18.0 g 1,4-butanediol ..

0.51 mol = 88.7 g of diisocyanate TDJ 80/20 i. * f ": ν

manufactured.,

The following test values were obtained:

Tensile strength / ~ kp / cm 7 Example 2 Comparison
attempt Elongation at break / ~% 7 J) J) O 70 Shore Α hardness _ _, 460 680 Rebound elasticity / ~% 7 80 - Permanent stretch
after J> 0 seconds f'fo 7 22nd - y 14 ■

Permanent elongation ■

after 60 minutes £ ~% _J2Y >

Comparative experiment: Without 2,2-bis (4-hydroxycyciohexyl) propane, but with 0.4 mol of 1,4-butanediol.

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- 26 -

'Mr "i i.-r« i c ^ "" ■

"Example 3

According to example i, a polyurethane was made from

Ο * 0 ^Γ > 0 t'ol - 100.0 r. ! ^! ? lyrfit'-T 'i; friüiß Hv 1-r ρ ic 2 i

Ο, ρ ^ ρ Hp ^{1 = 1} PPiP S polyester.according to example, 1.,. ,,,,,,. 0.150 mol = 51.6 g _: 4.4! -Bis (2-hydroxypropOxy) -diphenyl

0 ^ 250 mol = 44 ^ 8 g Diiso'cyanat TDJ 80/20 manufactured.

The following test values were obtained:

^ ■ rt'fclBfc.-t-.U. ; ·: Κν;: Μ.-. ^ Mi- kv --'- V ·:. ■ · «

Tensile strength 286 kg / cm

Elongation at break,.,., _. 480 ^ Permanent elongation after 30 seconds 1.3 %

Comparative experiment: see example 1 (second comparative experiment)

The. Two examples below point out as one of the possible Use cases the production of high quality threads according to, both from the solution as well as from the melt. These examples show at the same time that such, especially when the starting compound c is used according to the invention, are produced Polyurethanes can produce highly elastic moldings in a simple manner.

'»If. ft T r "i p 1" < . .

Example "4 '.

It became a polyurethane of the composition

0.100 mol = 200.0 g polyester according to Example 1 0.3QOMoI = 27 * 0 g butanediol-1,4

0.100 mol = 34 ^ 4 g of 4.4 ^l . -Bis (2-hydroxypropoxy) -diphenyi- .. _h; . . . dimethyl methane

0.516 moles = 89 ^ 8 g diisocyanate TDJ 80/20

.% cadmium stearate dissolved in the kneader in butyl acetate - with the addition of 5 wt ~% titanium dioxide (Anastatyp) and 0.5 wt.. A highly viscous solution of approx. 70% resulted.

009840/2255

- 2'Γ -

Using a plunger injection machine was injected at an injection head Tempera door of 6o ° C elastic threads, the pre-dried in a drying tunnel at first at 7O ⁰ C and finally at 136 - were completely dried 14O ° C.

The threads had the following properties:

Thread cross section 0.068 mm

Tensile strength 4 # 3J5 kg / min

Elongation at break 510 %

Permanent stretch after 30 seconds 6 %

Example 5
It became a polyurethane of the composition

1.0 mol = 2000 g of polyester according to Example 1 3.0 mol = 270 g of 1,4-butanediol

2.0 mol = J> 9k g tricyclodecanedimethylol (5.2, 1, 0, ² ' ^b ) 6.2 mol = 10o g diisocyanate TDI 80/20

produced in that the dehydrated and with 2 wt. % (based on polyester) stearic acid provided as a retardant diol mixture is ^{continuously mixed at 85 0} C with the corresponding amount of diisocyanate at a speed of the rotor in the mixing head of 5240 rpm and this mixture in approx. 30 kg bucket was injected. The output was 852 g / min. To complete the reaction, the reaction mixture was ^{heated to 100 °} C. for 18 hours. After cooling, a rubber-like product was formed which had a softening point of approx. 170-180 ° C. and formed a fur on the roller. The following test values were obtained:

009840/2255

201 3316 215 kp / cm 510 % 46 kp / cm 70 12th Si 4th 1

- 28 -

Tensile strength elongation at break

Stress at 300 % elongation Shore A hardness

Rebound elasticity Permanent elongation after 30 seconds Permanent stretch after 60 minutes

After granulating the material on a screw extruder, this polyurethane became elastic threads injected. The temperature in the screw area was 170-185 ° C and in the extrusion head 185-195 ° C. As a comparative experiment threads were made from a commercially available thermoplastic in the same way. Injected polyurethane. The threads had the following properties:

Example 5 comparative

attempt

Thread cross section / mm_7 0.045 0.092

Tensile strength / ~ kp / mm ² _7 7.86 3.38 Elongation at break / ~ ^ _7 580 650

Permanent stretch after

30 seconds ~ g_7 11 60

The following examples show that not only short-chain Starting compounds, but also those with Molecular weights between 1000 and 10,000, provided that they are atomic groups with a practically rigid link of at least two aliphatic and / or aromatic rings not lying in one plane, the Reduce the set of linear polyurethanes.

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- 29 - ■

Examples 6-9

The molar composition of the polyurethanes produced and their properties can be found in Table 1. ■ The comparative experiment associated with Example 6 has already been mentioned in Example 1, the second comparative experiment. (Comparative tests according to Example 7-9 result from experience as a result of the low urethane content softer polyurethanes with even higher permanent elongation.)

The polyester A or polyester B differs from the polyester according to Example 1 in that 1,6-hexanediol against tricyclodecanedimethylol (5 * 2,1,0 ') or against 4,4 ^l -bis (2-hydroxypropoxy) -diphenyldimethylmethane was exchanged, namely the exchange amount was in each case 2/3> mole fraction of the IX ^! component of the polyester. The hydroxyl numbers found were 52.2 and 52.6, respectively. As a result, the molecular weights were 2,150 and 2,150, respectively.

Example 9 shows the simultaneous use of a long-chain starting compound and a short-chain Starting compound according to the invention for the production of polyurethane.

009840/2255

Table 1: Examples 6-9. Molar ratio of the starting compounds and test values.

Example; 678

Polyester according to the example 1 0.5 4th - - 0.5 Polyester A 0.5 mm 1 - - Polyester B - 5.16 - 1 0.5 1,4-butanediol 240 3 2 1.5 Tricyclodecane dimethylol
(5,2,1,0, ² ' ⁶ ) 570 _ 1.5 Diisocyanate TDI 80/20 48 4.12 3, io 4.12 Tensile strength / kgf / cm ² y 63 120 106 210 Elongation at break / ~ # _7 14th 490 375 530 Voltage at ₂
300 % elongation / kg / cm_7 4.2 65 28 29 Shore A hardness 0.6 80 90 78 Rebound resilience / ~ £ J 26th 26th 25th Permanent stretch
after 30 seconds P-IoJ 8.2. 4.8 3.0 Permanent stretch
after 60 minutes f ~% _7 5.0 0.6 0

The following examples show that the considerable- ■ lent reduction in permanent deformation and the usually also considerable improvement in tensile strength on the chemical structure and the quantitative ratio (with equivalence of diol and diisocyanate) of the other starting compounds used for the preparation of the polyurethanes according to the invention practically independently is.

009840/2255

Example 10

As in the following examples, one thermoplastically processable polyurethane was made using another Diisocyanate produced:

0.10 mol = 200 g polyester according to Example 1

0, ^ 0 mole = 59 g tricyclodecane dimethylol (5.2, 1, 0, ² ') 0.41 mole = 103 S 4,4'-diphenylmethane diisocyanate

Table 2 shows the properties of this polyurethane. The table also shows the results of the comparative tests carried out, in which the tricyclodecanedimethylol by equimolar amounts the specified diols was replaced.

Table 2; Example 10 and comparative experiments for two

game ίο , Test results. Ethylene
glycol Pentane
diol
1.5 Hexane
diol
1.6 Low molecular weight
Diol Tricyclo
decandi
methylol 113 129 127 Tensile strength
^ kp / cir fj 145 300 515 410 Elongation at break f ~% 7 400 60 85 90 Shore A hardness 70 12th 38 30th Permanent stretch
after 60 minutes / ~% 7 ι

Examples 11-19

The molar composition of the polyurethanes produced is shown in Table 3. As a long-chain starting compound In addition to the polyester according to Example 1 and the PolycaprolacLon according to Example 2, a polypropylene glycol ether with the average molecular weight 1044 (Example 17) and one with the molecular weight;

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- 32 -

2070 (Example 18) used. In addition, various diisocyanates, both aliphatic and aromatic, in the last example as a mixture. In Example 14, two different Starting compounds each with different atom groupings, which by a practically rigid Linking of two aliphatic or aromatic rings not lying in one plane are formed, used.

_o : table 3; Examples 11-19. Molar ratio of starting compounds

Example; . '11 12 * 1? 14 15 16 17 18 polyester according to

Example 1 1.0 1.0 1.0 1.0 * - - 1.0 Polycaprolactone - - - - 1.0 1.0 Polypropylene glycol

ether - 1.0 1.0 -

Butanediol-1.4 3.0 2.0-1.0. - 1.0 1.0 3.5 2.0 Hexanediol-1,6 - - 2,0 - - - - - Tricyclodecanedi-

methylol _o r

(5,2,1,0, * '°) 1.0 - 2.0 1.0 2.0 - 1.0 3 * 5 2.0

in} 4,4 '-bis (hydroxy-
- ethoxy) -diphenyl-

dime t hy lme than - - - 1.0 - 3.0 - - 4,4'-bis (2-hydroxyi

propoxy) -diphenyl-

dimethylmethane - 5.0 - - -

Diisocyanate TDI
(80/20) - - 5.2 4.2 - 5.4 3.1 - -

Mixture of isomers

1.3- and 1.4-

Xylylene diiso-

cyanate (70/30) 5.2 - _-._-_- isomer mixture from

2,2,4- and 2,4,4-tri-

methylhexamethylene

diisocyanate - 8.2 - ______

4,4'-diphenylmethane

diisocyanate - - _ 3.1 _ _ 8.0 2.5

Isophorone diisocyanate- - - - -.I 2.7

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Comparative experiment: carried out with a corresponding amount of 1.6-hexanediamine.

Examples 23 and 24

The molar composition of the polyurethanes is shown in the table. In these examples, hindered diamines were used of group C) is used. The test results can be found in the table.

Table 7 » Examples 23 and 24. Molar ratio of the starting compounds.

Example 23 24

Polyester according to example 1

3.3'-dimethoxy-4.4-diaminoo.6'-dichloro-di phenyl

2.2'.5.5'-tetra-chloro-4.4'-diamino-diphenyl

Diisocyanate TDJ 8o / 2o

Table 8; Examples 23 and 24. Test values determined.

1.00 l, oo l, 2o - _ l, 4o 2.28 2.48

example 23 Compare :: s-
attempt 24 Comparative
try Tensile strength
ability Jcp / em £. · 165 84 145 4o Elongation at break
/ X7 46o 320 430 2I0 Permanent elongation ^
after 30 SeIc. ./.#_/ 8th 17th 8th 2o Permanent stretch
after 60 min. / _% _j \ 11 4th

Comparison vesuc.; E: carried out with corresponding molar amounts Hexandiaini n> 1.1.

009840/2255

Claims (1)

Claims ο · γ Process for the production of uncrosslinked, linear O-polyurethanes by reacting a) bifunctional, hydroxyl and optionally amino groups and / or mercapto groups, preferably compounds containing two hydroxyl groups with molecular weights between 1000 and 10,000, preferably 1500 to 2000, or mixtures of such compounds , b) aliphatic and / or aromatic diisocyanates and c) bifunctional. Hydroxyl, amino and / or mercapto groups - preferably compounds containing two hydroxyl groups with molecular weights below 1000, preferably below 500, or mixtures of such compounds, characterized in that starting compounds a, b and / or c are partially or completely used which contain at least have an atomic grouping which is formed by a practically rigid linkage of at least two aliphatic and / or aromatic rings which are not in one plane. 2) Method according to claim 1, characterized in that starting compounds a, b and / or c are used that have at least one polycyclic bridge ring system contain, which can also have one or more heteroatoms. 3) Method according to claim 1, characterized in that that starting compounds a, b and / or c are used which contain at least one sterically hindered atom group the formula 009840/2255 aliphatic and / or aromatic rings that do not lie in one plane are used or are used as reactive functional groups hydroxyl, amino and / or Mercapto groups, preferably hydroxyl groups, contain. 9) Uncrosslinked, linear polyurethanes made by Implementation of a) bifunctional, hydroxyl and optionally amino groups and / or mercapto groups, preferably two hydroxyl-containing compounds with molecular weights between 1000 and 10,000, preferably 1,500 to 3,000, or mixtures such compounds, b) aliphatic and / or aromatic diisocyanates and c) bifunctional, Hydroxyl, amino and / or mercapto groups - preferably two "hydroxyl groups - containing compounds with molecular weights below 1000, preferably below 500, or mixtures of such compounds, characterized in that that in their preparation partially or completely such starting compounds a, b and / or c have been used, which have at least one atomic grouping, which by a practically rigid linkage of at least two aliphatic and / or aromatic not lying in one plane Wrestling is formed. 10) Uncrosslinked, linear polyurethanes according to claim 9 »characterized in that they are polycyclic in the molecule Contain bridge ring systems, which can also have one or more heteroatoms. 11) Uncrosslinked, linear polyurethanes according to claim 9 »characterized in that they are steric in the molecule hindered atomic groupings of the formula 009840/2255 contain, the rings X and Y at least 5-membered, are preferably 6-membered, and aliphatic and / or aromatic, one or more May contain heteroatoms, and where. · A) a ~ 0-, -8 -, .- SO-, -SOg-, -CO- or -CHg- group means and at least one of the radicals R is an alkyl group with 1-18 carbon atoms, a cycloalkyl or an aryl group (which groups also have an oxygen or sulfur atom on the ring X or Y can be bonded), a dialkylamino group with 2-24 C atoms, a nitro group or is a halogen atom, while the other radicals R are hydrogen atoms, or where also all radicals R can be hydrogen atoms, provided that the rings X and Y are aliphatic and Z denotes a -0-, -CO- or -CHg group, B) Z is a -CHR ₁ - or -CR ^ Rp group, in which R ₁ or R ₁ and R _{g are} each an alkyl or cycloalkyl radical with 1-12 carbon atoms or R. and Rg are a common cycloaliphatic ring lind the radicals R have the meaning given under A) or all radicals R hydrogen atoms are or C) the rings X and Y are directly connected to one another and the radicals R have the meaning given under A) or all radicals R can be hydrogen atoms, provided that the rings X and Y are aliphatic are. 009840/2255 12) uncrosslinked, linear polyurethanes according to claim 9 to 11, characterized in that they contain sterically hindered atom groups in the molecule according to claim 11, B), where R, and / or Rp denotes a cycloalkyl radical with at least one polycyclic bridge ring system or R, and Rp represents a common cycloalkyl radical with at least one polycyclic bridge ring system. Uncrosslinked, linear polyurethanes according to Claims 9 12, characterized in that they are in the molecule Contain sterically hindered atom groups, in which the rings X and / or Y are a cycloalkyl radical mean with at least one polycyclic bridge ring system. 14) uncrosslinked, linear polyurethanes according to claim 9 13, characterized in that they contain at least two different atom groupings in the molecule, which in each case by a practically rigid connection of at least two not in one Aliphatic and / or aromatic rings lying flat are formed.